Process for treating materials and products produced



. Patented a. 21 1941 PROCESS FOR TREATING MATERIALS AND PRODUCTS PRQDUCED James Andrew Clark, Port Chester, N. Y., assignor to Sylvania Industrial Corporation, Frederictoburg, Va... a corporation 0! Virginia No Drawing. Application December 30, 1939,

a Serial No. 311,815

materials. In particular it relates to amethod for printing and dyeing textile fabrics and the articles so produced, and to correlated improvements designed to enhance the properties and to increase the utility of'such products.

Heretofore, textile fabrics have been printed with pastes comprising'a dyestufl thickened with "aqueous dispersions of starches, gums, resins,

water-soluble celiulose ethers and the like. These thickening agents have been found not to 'be' entirely satisfactory because they are soluble;

in water in' the final product and wash out of the fabric upon laundering and so permit substantial amounts of the dyestufl to become dissiyond the printed areas.

It is an object of the invention to provide a method for coloring sheet materials to improve their decorative appearance, and in particular to-provide a method for the printing of textiles so that the coloring matter is permanently anchored to the textile.

It is a specific object of the invention to pro- -duce novel and descriptive color and 'surface efiects on sheet materials such as textiles .and

the like, and to produce color and surface effects which-are resistant to bleeding and crocking and which are fast to laundering, and which are substantially permanent in character.

It is a further object of the invention to pro- .vide textiles having dye-printed areas of sharp definition, greater depth and permanency.

other objects of the invention will in part beobvious and will in part'appear hereinafter.

According to the present invention sheet mate-- rials such as textiles, papers, foils are colored by applying thereto a composition comprising an undeveloped dyestuil component, a carrier for the dyestuff component comprising a coagulable cellulosic colloid, a dispersion medium for the cellulosic colloid, and treating the sheet mate- 'rial with a developer for the undeveloped dyestui! component and a coagulant for the cellu losic carrier, whereby the water-insoluble carrier permanently binds the developed dyestufi' to the sheet material.

The term undeveloped used in connection with the dyestufl component includes dyestuils which may exist in an undeveloped, not fully colored or latent state and which are capable of yielding a colored substance by reaction with pated.- Moreover, such agents do not prevent the diffusion of a solublecoloring matter bea known chemical reagent or by 'a change in cong i 8 Claims. (01. 8-62) This invention relates to the coloring of-sheet ditions of the medium such as hydrogen-ion concentration and/or temperature.

The term "developer designates not only such dyestud components as coupling agents, diazo compounds, amines, bases and the like which will react with an undeveloped dyestufl to yield a colored substance, but also agents which will change the conditions and cause a development of color in the undeveloped dyestuii, as for example acids, bases, oxidantsyheat and combinations there'oi. which will eause, permit or facilitate a stabilized dyestufl component or an undeveloped or latent dyestuii component to 'yieid'a colored substance.

The invention accordingly comprises novel products possessing the characteristics, properties, elements andthe relation of elements, and a process having the steps and relation of steps,

all as exemplified in the following detailed disclosure and the scope of the application oi'which will be indicated in the claims.

In its broad aspects the invention comprises three embodiments. In one embodiment a sheet material, such as a fabric, is treated in predetermined areas with an undeveloped dyestufi component dispersed in a, carrier comprising a coagulable cellulosic colloid and a dispersion' medium for the colloid, and the fabric treated with a coagulant for the carrier and a developer for the undeveloped dyestufi component thus insolubilizing the cellulosic colloid and developing the dye in situ on the fabric.

The second embodiment constitutes substantially a reversal of the steps employed in the.

first embodiment. Instead of the undeveloped dyestuiicomponent being dispersed in the cellulosic carrier, a developer for the dyestuii is dis-. persed in such carrier. A fabric printed with such composition is then treated witha coagulant tor the cellulosic carrier and with an undeveloped dyestuii' component which reacts with the developer to form a colored dye in situ.

In a third embodiment, a sheet material is.

treated, as by printing, with a composition comprising a stabilized dyestufl. in an undeveloped and/or colorless form (which stabilized dyestui! comprises two or more separate dyestufl' com- 'ponents), a carrier for the stabilized dyestufl comprising a .coagulable cellulosic colloid initially solubleinwater and a dispersion medium for the cellulosic carrier. The treated material is next treated with a coagulant for the carrier and with an agent which unstabilizes thegdiie stuil' thus permitting or causing a colored dye to be formed. In this embodiment, the coagulant tains a cellulosiccarrier which is initially soluble (i. e. dispersed in a fluid medium), whereas the final product comprises a deposit .of colored material bound to the sheet material by a waterinsoluble cellulosic colloid.

In preferred forms of all the above-mentioned embodiments the carrier is coagulated and the color developed in the same bath, whether with the same or with different reagents.

The process is applicable for coloring sheet materials of various kinds," such as the fibrous sheet materials as well as the non-fibrous -foils such as Cellophane. In. particular, the process is applicable for coloring textiles, felts and papers, all formed from natural fibres such as cotton, flax, ramie, Jute, silk, wool and the like.

Textiles, felts, papers and foils formed from' artificial materials may likewise be employed in the invention such, for example, as those ma terials and structures formed from cellulose, which may include regenerated cellulose or cellulose hydrate, the cellulose ethers, such as alkyl cellulose ethers, aralkyl cellulose ethers, hydroxyalkyl cellulose ethers, carboxy-alkyl cellulose ethers and'the like; the cellulose esters, such as nitrocellulose, cellulose acetate, formyl cellulose and the like; ether-esters of cellulose, resins of all kinds, and from mixtures of these classes of.

substances, also textiles and-papers made from mixtures of difl'erent kinds of ilbres.

The carrier for the. dyestufl component may comprise suitable coagulable cellulosic colloids, such, for example, as alkali-soluble cellulose ethers. I

The cellulose ethers which may. be used as the carrier comprises the alkyl ethers of cellulose, the hydroxy-alkyl cellulose ethers, the carbcxy-cellulose ethers, the mixed ethers, and the like, which are-initially insoluble in water but soluble in aqueous solutions of alkalies.

Theundeveloped dyestuif component of the of dyes known as the naphthols." In place of using a base as theundevelopeddyestuii', an amine may be substituted therefor and then diazotized'andcoupled with a suitable base in a known manner to form a dye.

The stabilized dyestuil! materials which may prise any of the compounds described in an article entitled Chemical Constitution of the Naphthol AS Type Dyes, by Kenneth L. Dorman, American Dyestufl Reporter, February 20, 1939, pages 7, 8 and 9. Suitable compounds are sold under the trade names of Rapidogens, Rapidozols, Diagens, Pharmasols and the like, all of which may be transformed into developed dyes by treatment with an unstabilizing agent, such as steam or acid.

Examples'of the reduced dyestuffs which'may be used arethe vat dyestufls, the Indigosols and the like which may exist in a reduced state and which may be transformed and brought to full color value by further treatment, such as by oxidation or steaming.

The composition of the invention, comprising a dye component dispersed in a colloidal celluiosic carrier may be applied to the sheet material by suitable methods known to the art as, for. example, by printing, dipping, spraying and the The coagulant for the cellulosic'carrier is se-- lected having regard for the nature of the particular celiulosic colloid employed. For the-alkali-soluble carriers, the coagulant may comprise an aqueous solution of sulphuric acid, acetic acid, hydrochloric acid, and the like. In particular, for alkali-soluble cellulose ethers, the zoagulant may be an aqueous solution of a salt, uch, for example, 'as sodium chloride, potassium sulphate, sodium bisulphite, and the like.

When the cellulosic carrier is a viscose soluticn,'

. the coagulant may be heat, an acid, a salt, or

. may be coagulated by heat, or by the use of reactions with naphthol bases form the family be used as the undeveloped dyestufl. component 1 comprise active stabilized diazo compounds which can be stored for certain lengths of time as a dry powder, either alone or mixed in dry form with the cellulosic carrier of the invention.

'I'he'classes of active and passive" stabilizeda mixture of acids and salts, as known to the art. The carboxy-alkyl cellulose ethers may be insolubilized by coagulating them in aqueous solutions of salts of aluminum, lead, tin, zinc, barium, calcium and the like, the metal salt reacting with the cellulose ether to produce a waterinsoluble metal salt thereof. The cellulose ethers water or aqueous solutions. A single agent, such as steam, may be employed simultaneously to coagulate the cellulosic carrier and develop the undeveloped dy component, as, for example; where a paste comprises an undeveloped leuco vat dyestuii dispersedin a heat-coagulable cellulosic carrier, such as a cellulose ether. The sam steam treatment inaywalso be employed when using the, passive" stabilized compounds which have been dispersed in a heat-coagulable carrier. I

4 iting the invention, the following examples are given:

' Example I Two solutions were preparedas follows:

' Solution A.-A solution comprising 2.5 gra.

hydroxy-ethylcellulose (alkali-soluble type) dilsolved in 4 grs. sodium hydroxide in ccroi water was prepared and 2.4 gm. beta-naphthol was fast to laundering.

essence (2-hiydroxynaphthalene) were dissolved in this solution. This composition was then printed onto a cotton fabric. v

SolutionR-Gh grams para-nitroaniline (1- I amino i-nitrobenzene) were dissolved in a solution comprising 12 grams of water and 14 grams of concentrated hydrochloric acid heated to a slightly elevated temperature. This was added to a beaker containingabout 70 cc. cold water and about 30 grs. of ice. A solution containing 3.6 grams sodium nitrite dissolved in 50 cc. of

water was then slowly added. To this mixture, 10 grams of sodium acetate dissolved in 50 cc.

I of water were added, whilestirrin'g. and this entire mixture brought-to a total volume of 300 cc. by adding cold water.

The cotton fabric printed with Solution A was then passed through Solution B. The cellulose ether carrier thereupon was coagulated and at the same time the dyestuff component was dlazotized to form a dye in situ. The fabric was then dissolved in a 4 per cent solution of'sodium hy- L droxide.

Solution B.,3.6 grams-sodium nitrite were dissolved in 250 grams of water at about 50.F 7.0 grams of hydrochloric acid dissolved in 25 grams of water was then added. To this solutionir was added sufficient sodium acetate dissolved in water to convert the free hydrochloric acid to free acetic acid, determined asbeing neutral to Congo red. and also to make a solution of approximately 300 cc.

A cotton fabric was then printed with Solution A and immediately soaked in Solution B for approximately 10 minutes.

SolutiocQ-iiil grams of beta-naphthol were dissolved in 4 grams of a 50 per cent sodium hydroxide solution, and then diluted to 300 cc. The fabric from Solution B was then passed into Solution C and allowed to remain therein about 5 minutes- The fabric was then withdrawn, washed and dried. The printed area of the material developed into a permanent deep red dye. The carrier remainedinsolub lld permanently fixedtothe fabric.

Example III A dyestuff known as Rapidogen Red GS (ortho-toluidide of beta-oxy-naphthoic acid, and the stabilised nitroso amine of 5-chloro-orthotoluidine). was wet out with a wetting agent and then mixed with a solution of hydroxy-ethyl cellulose dissolved in a sodium hydroxide solution. Cotton fabric was printed with this paste and allowed to partiallydry. The fabric was then passed into a dilute aqueousaceticacid solution which simultaneously coagulated the cellulose ether and developed the-color. The fabric was finally washed and dried. .It was thenscoured in soap and soda ash solution for several minutes atan elevated temperature. It was found that at no time did the color bleed. Furthermore, the fabric showed exceptionally good color. value and Example.

, solution oi'beta naphthol were A ange solution.

"grams of 864mm h droxmess' grams of water and 5 grams of suli'onated castor oil. 1

A cotton cloth was padded all over with the. above Solution A and then dried at low temperature.- l

Solution B.-3grams oi para-nitroaniline' (1- amino-4-nitrobenzene) was dissolved in grams 'of water containing 8 grams of concentrated hydrochloric acid. This mixture was thenwarmed until completely dissolved. and then cooled to 50 F. whereupon the dissolved para-nitroaniline hydrochloride precipitated. Next 1.5 grams of sodium nitrite in 10 grams of water were added to the above preparation, which redissolved the para-nitro-aniline hydrochloride to form an or- Solution C.A solution comprising 6 per cent alkali-soluble'cellulose ether'Wiscosity 6) and 4 per cent sodium hydroxide then was prepared.

cc. of Solution B was then slowly added to cc. of Solution C while stirring, in such a 1 manner as'to prevent local coagulation; No precipitation of the cellulose ether takes place due to the vigorous stirring and low acid concentration. The mixture becomesbrown.

The cloth next was printed withthis comp0- sition, and then exposed to steam containing va-' pots of acetic acid which developed the dyestuif and coagulated the cellulose ether, yie ding sharp red prints with well-defined edges w ch are resistant to laundering because the insoluble cellulose ethenbinds the dyestufl to theI-fabric.

The article of the invention maybe varied by agentsyjwaterprooilng agents,

with a composition of the invention upon a fabric which-has already been given an all-over treatment with a dyestufl. and then passing the entire fabric into the developer and coagulant. Alternatively, a sheet material may begivenapreliminary treatment with resists, and then all over or in predetermined areas according to the invention to provide untreated areas upon re- ,moval of the resists.

- prints having sharply defined edges. The prints.

As a result of the process disclosed inthe invention, there is produced articleicomprising a sheet material having a deposit of colored material thereon. Since the ,cellulosic carrier is insoluble in water and binds the .dyestufl to the sheet material, the colorationishighly'resistant to wear or laundering and the leaching of the dyestuif is substantially prevented.

- Since the cellulose ether usedinthe invention is of a substantially insoluble nature, the fabrics treated according to the invention will bear are not subiect'to bleeding, crocking and similar limitations encountered in the dyeing and printing industry. The dye is developed in' the cellulosic deposit with which the fabric isimpregnated, as well as in the fabric in sitm and'thus becomes fastened to the fibres in the fabric as o well as to the cellulosic deposit.

Unusual optical eii'ects are produced 'in a fabric by the method disclosed in the invention. due to the combined refractive indices of the cellulose ether and the dyestuii'.

Another novel characteristic of the product is the fact that the deposit: of cellulose ether tends to stiifen and/or improve the hand and feel of ,the material where applied in contrast to the unwet out and dissolved in a solution containing 8 treated areas. Thus, the article has a better hand, surface appearance and a better color value.

Since certain changes may be made in the above process and product produced utilizing the same, and different embodiments of the invention could be made without deterring from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended. to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. I

Having described my invention, what I claim as new and desire to secure by Letters Patent is:

-1. In a process for treating materials, the steps comprising printing a material with a composition comprising an undeveloped dyestufl component and a cellulosic carrier for said undeveloped dyestufl component comprising a coagulable alkali-soluble water-insoluble cellulose ether dispersed in liquid medium, treating the material with a coagulant fbrthe cellulosic carrier and a developer for the undeveloped dyestufl component, the coagulated carrier being water-insoluble. and binding the dye-stuil.

2. In aprocess for treating textile materials, the steps comprising printing a textile in predetermined areas with a composition comprising an undeveloped dyestufl component, a cellulosic carrier for said undeveloped dyestufl component comprising a coagulable alkali-soluble water-insoluble cellulose ether, a dispersion medium for rier for said dyestuff component 'comprising a coagulable alkali-soluble water-insoluble, cellulose ether, a-dispersion medium for said cellulosic carrier, treating the material with steam to coagulate the cellulosic carrier, and a developer to develop the undeveloped dyestuif component, the coagulated carrier being water-insoluble and binding the dyestuff.

5. In a process for treating materials, the steps comprising printing a material in predetermined .areas with a composition comprising an undeveloped dyestufl component, a cellulosic carrier for said dyestuff component comprising a coagulable alkali-soluble water-insoluble cellulose ether, a solvent for said cellulosic carrier comprising an aqueous solution of caustic alkali,

treating the material with a liquid which will cosaid cellulosic carrier, treating the material with said cellulosic carrier, and thereafter simultaneously treating the material with a coagulant for the cellulosic carrier and a developer for the undeveloped dyestuflcomponent, the coagulated carrier' being water-insoluble and binding the yestuff.

3. In a process for treating textile materials,

steps of printing a fabric with a composition comprising an undeveloped dyestuif comprising dye ingredients in a stabilized condition, a cellulosic carrier for the undeveloped dyestuif comprising coagulable alkali-soluble water-insoluble the steps comprising printinga textile in prede- I termined areas with a composition comprising an undeveloped dyestufi component, a cellulosic carrier for said undeveloped dyestufl component comprising a coagulable alkali-soluble waterdnsoluble cellulose ether, a dispersion medium for said carrier, treating the textile in predetermined areas with a substance having the combined function of being able to coagulate the cellulosic carrler and develop the undeveloped dyestufi component, the coagulated carrier being water-insoluble and binding the dyestufl,

cellulose ether, a dispersion medium for the said carrier, thereafter treating the fabric with a coagulant for the cellulosic carrier and a developer to permit the dye ingredients to react with each other, the coagulated carrier being water-insoluble and binding the dyestuflf.

8. In a process for treating textile materials the steps comprising padding a material all over with a. composition comprising an undeveloped dyestufi component, printing the material in predetermined areas with a composition comprising a second undeveloped dyestufl component dispersed in a coagulable alkali-soluble water-insoluble cellulosic colloid and a solvent for said colloid, treating the material with a substance having the functionof being able to coagulate the cellulosic colloid and develop the dyestufl, the coagulated carrier being water-insoluble and binding the dyestuif.

J. ANDREW CLARK.

. V 7 CERTIFICATE 0F coRREcTIoN .-J Patent No. 2,259,796; 1 October 21, 1914.1

I JAMES ANDREW CLARK;

It is hereby eertified that-error appears in the printed specifieation of the above numbered patent requiring r iqn as follows: Page 1 first column, line 28, claim l, 'for-"dye-stuff" read -.dyestuff--; and second column, line 2-, claim'li, after"'water-insoluble" strike out the comma; and that the said Letters Patent should be read with this cerrection therein that the same may conform to the record of the case in the ,Patent Offi'ee.

Signed and sealedthis 2nd day of Decahber, A. Da'l9hl.

H Henry Van Arsdale, (Sea1) Acting Commissioner-pf Patents. 

